Esteramides



Patented Apr. 10, 1945 UNITED. STATES PATENT orcs- $233... Melvin DeGroote, University City, and-Bernhard Keller, Weblter Groves, M

o., are to Petroiite Corporation, Ltd, ,Wiimington, no,

a corporation of Delaware No Drawing.

10 Claims.

Original application December 27,- 1941, Serial No. 424,649. Divided andthis application July 1, 1943, Serial No. 493,161

, (Cl- 260-404) I This invention relates to a new chemicalprodpracticable methodfor making said new compound or composition ofmatter.

The new chemical product or compound which constitutes our presentinvention, consists of a ,sub-resinous or semi-resinous product obtainedby reaction between a polybasic carboxy acid or its equivalent, such asthe anhydride, and a hydroxylated esteramlde of the kind hereinafterdescribed; Said hydroxylated esteramide is of the kind in which theamido acyl radical is derived from amono'carboxy acid having not over 5carbon atoms and the oxyacyl radical is characterized by being derivedfrom a, monocarboxy' detergent-forming acid having at least 8 and notmore than 32 carbon atoms.

It is well known that certain monocarboxy organic acids containing 8carbon atoms or more,- and not more than 32 carbon atoms, arecharacterized by the'fact that they combine with alkalies to producesoap or soap-like materials.

These detergent-forming acids include fatty acids, resin acids,petroleum acids, etc.- For the sake of convenience, these acids will beindicated by the formula R'COOH. Certain derivatives ofdetergent-forming acids react with alkali to proamides derived fromhigher fatty acids, rather than petroleum acids, rosin acids, and thelike. 'We-have found that by far the most eflective demulsifying agentsare obtained from unsatu- 1 rated fatty acids having 18 carbon atoms.The

higher fatty acids include unsaturated fatty acids, such as oleic acid,ricinoleic acid, linoleic acid, linolenic acid, etc. One may employmixed fatty acids, as, for example, the fatty acids obtained byhydrolysis of cottonseed oil, soyabean oil, corn oil, etc. our preferreddemulsifler is obtained from unsaturated fatty acids, and moreespecially,

unsaturated fatty acids containing a hydroxyl radical or unsaturatedfatty acids which have been subjected to oxidation or oxyalkylation,such as oxyethylation. V

The esteramidesof the kind herein described may beobtained inanyconventional manner.

- They are usually derived from the low molai acids themselves; but ifdesirable, the functional equivalents, such as the anhydrides, acylchlorides, or other derivatives, may be employed. Suitable acidsinclude, of course, acetic acid, propionic acid, butyric acid, valericacid, etc. The amide of such low molal acid may be treated with anoxyalkylating agent, such'as' ethylene oxide, propylene oxide, butyleneoxide. or the like, so as to produce a compound ofthe following type:

c alkylene.0H

I alkyIenaOH Actually, the alkylene radical might represent anequivalent divalent radical, in which the carbon atom chain isinterrupted at leastonce by oxygen, as

duce soapor soap-like materials, and are the obvious equivalent of theunchanged or'unmodifled detergent-forming acids; for instance, insteadof fatty acids, one might employ the chicrinated fatty acids. Instead ofthe resin acids. one might employ the hydrogenated resin acids. Insteadof naphthenic acids, one might employ brominated naphthenic acids,'etc.

The fatty acids are of the type commonly're-- ferred to as higherfattylacids; and of course, this is also true in regard to derivativesof the kind indicated, insofar that such derivatives are obtained fromhigher fatty acids. The petro- -c=moc= m- Having obtained ahismrdroimikymmme or the kind described, such compound then be reactedin a conventional manner with a high molal acid or itsequivalent, togive an esteramlde,

in other words, a compound of the following type: I

A procedure that is freduently more readily leum acids include not onlynaturally-occurring naphthenic acids, but also acids obtained bytheoxidation of wax, paraiiin, etc. Such acids may have as many as 32carbon atoms. For instance. see U. 8. Patent No. 2,242,837, dated May20, 1941, to shields.

, Although-any of the high molal monocarboxy acids can be convertedintoesteramides of the kind described, by conventional procedure, it isour preference to employ hydroxylated ester adaptable is simply thereaction between a low molal acid, such acetic acid, and a material ofthe kind exemplified by .diethariolamine, di-

propanolamine, or the like.- For the sake of brevity, referencehereafter will be made-largely.

to diethanolamine' and acetic acid, although other suitable reactantshave already-been described. The method of manufacturing ester-- amides.isso well known that no'further description is required; butforconvenience, the following example is given in substantially verbatimform, as it appears in U. 8. Patent No. 2,238,928, dated April 22, 1941,to Calm and Harris:

Example A (1) 224 grams of methyl acetate -(3 moles) and 210 grams ofdiethanolamine (2 moles) were mixed together, two layers forming atfirst, the mixture becoming a homogeneous mass after a short time. Themixture was refluxed for 19 hours, at which time 90% of thediethanolamine had reacted. A portion of the reaction mixture wassubjected toa vacuum of 6 millimeters at 60 0., in order to drive of!the volatile material, i. e., the unreacted methyl acetate and themethyl alcohol which was formed during the reaction. The residue, upontitration, showed a content of 4.64% of free diethanolamine. To 192.5grams of this residue, 34.? grams of methyl acetate were added and themixture was refluxed for-3V2 hours. The resulting reaction product wasthen freed from its low boiling constituents, i. e., the methyl alcoholand unreacted methyl acetate, by maintaining the mass at 70 0., under, apressure of ,6 millimeters. The residue contained approximately 0.8% ofunreacted diethanolamine, based upon a determination of the alkalinityof said residue by titration. The product was a light yellow coloredsyrup, soluble in water, and contained a compound which was essentiallythe acetic acid amide or diethanolamine, having the following formula:

CrHiOH em-o-N g CiHiOH (2) 51.0 grams We mole) oi the acetic acid amideof diethanolamine produced as described in part 1 hereof, and 38.0 grams/s mole) of lauric acid were heated together for minutes atapproximately 200? 0., while passing carbon .40.

dioxide gas through the reaction mixture. At

I the end of the 15 minutes, the free lauric acid had I Illustratingsomewhat similar types of reactions, see (U. S. Patent No. 2,238,902,dated April 22, 1941, to Katzman and Harris, and also U. 8. Patent No.2,257,183, dated April 30, 1941,- to Munz and Troskan) 1 In view of whathas been said, it will be obvious -that hydroxylated esteramides of thekind herein employed as reactants, may be obtained in various manners,including those described in the patents previously, mentioned. Asillustrating such hydroxylated esters, reference is, made to thefollowing formulas:

' o cimoooa'on o cimooca" aa i 0 c-moooa'on \RHI O- CiHiOOCR" tn CIHIOOC R'OH In the above formulas, RCO represents the acyl radical derivedfrom an acid having 5 carbon atoms or less, such as acetic, propionic,butyric. etc. OHR'CO represents the acyl radical of a hydroxylated acid,such as ricinoleic acid, hydroxystearic acid, or similar acids obtainedby oxidation, such as blown oleic acid or acids obtained by thehydrolysis of blown olein. Such acyl radicals all contain at least 8 andnot more than 32 carbon atoms and are apt to contain 18 carbon atoms.rived fromv a non-hydroxylated monocarboxy detergent-forming acid,particularly an unsaturated acid, such as oleic acid, linolenic acid,etc. It is understood, of course, that a mixture of fatty acids might beemployed instead of a single fatty acid. R' is a hydrocarbon radicalhaving 4 to 12 carbon atoms.

In examining the above formulas, it is to be noted that comparableproducts might be obtainable from monobutanolamine, dibutanolamine,monopropanolamine, dipropanolamine, monoglycerylamine, -diglycerylamine,or the like, instead of being derived from 'monoethanolamine ordiethanolamine. Similarly,

the products shown-in the last two formulas are derived fromtris(hydroxymethyl) aminomethane. derivatives may be derivedfrom2-amino-2-ethyl- 1, 3-propanediol and 2-amino-2-methyl-l, v 3propanediol.

The hydroxylated esteramides may, of course, be derived in any othersuitable ,way, such as reaction with ammonia, followed by oxyethylation,

or some other suitable process. Thus, the low molal acids themselves,or, if desirable, the functional equivalents, such as the anhydride's,acyl chlorides, or other derivatives, may be reacted with ammonia, or aprimary amine, such as any suitable alkylamine, or an alicyclic amine,or an aralkylamine, to give the amide or substituted amide; in anyevent, a compound containing at least one amino hydrogen atom. Suitableamines include butylamin'e, amylamine, octylamine, decylamine,eyclohexylamine, benzylamine, phenylamine, etc. Generally speaking,-whenan amine is used instead of ammonia for reaction with-a low molal acid,one must employ a hydroxylated detergent-forming acid, such asricinoleic acid, in

' order to insure anavsilable'sicoholic hydroxyl group for subsequentreaction with the polybasic R"CO is the acyl radical de- SimilarActually, the alkylene voiving acetic acid and butylamine. Thesubstituted amide so obtained can be treated with I ethylene oxide, andthen reacted with oleic acid to give a substituted esteramide.Suchsubstituted esteramide, however, is not reactive toward phthalicanhydride by esterifleation reaction, in

view of the absence of an alcoholic hydroxyl radical. If, however,ricinoleic acidis employed as the reactant to supply the high molaloxyacyl radical,v

then the hydroxyl radical which is part of the ricinoleyl radical wouldserve as a reactive function for combination with phthalic anhydride' orthe like by esterification. Lactic acid or the like might supply analcoholic hydroxyl radical.

An alternate procedure, in case such compounds are derived frombutylamine, cyclohexylamine, benzylamine, or the like, is to use glycidor the like as an oxyalkylating agent, thus introducing at least twohydroxyl radicals, one of which may be employed for esteriflcation withOleic acid, and the other one, for esteriilcation with phthalic acid orthe li The simpler procedure is to prepare the amide from ammonia, andsuch amide of a low mo'al acid may be treated with an oxyalkylatingagent,

such as ethylene oxide, propylene oxide, butylene oxide, sly id, or thelike, to produce a compound of the following typ I 0 alkylehe-Oih m malkylgemi OH equivalent divalent radical-in which the carbon atom chainis interrupted at least once by oxygen;

1. e., the low molal amide, instead of being treated with two moles ofethyleneoxide or the like, might be treated with four moles or sixmolesof ethylene oxide, or even more.

In any event, the reaction of the hydroxylated esteramide of the kinddescribed with a polybasic radical might represent an carboxy acid orits functional equivalent, such as fthe anhydride, is a. well knownreaction and is nothing more -or less than an esteriflcation reaction ofthe kind employed to produce phthalated eastor 'oil, phthalatedricinoleoamide, etc. For instance, common comparable reactions aredescribed in U. 3. Patents No. 1,976,602, to De Groote, Kaiser, andAdams, datedOctober 9, 1934.

shop; :5. Patent No. 2,078,652, to DeGroote and- Kaiser, dated April 27,193']. I

Briefly stated,, the molar combinations of the reactions selected dependupon the available number of hydrox'yl' groups and may be illustrated bythe following examples: J

- Example 1 One pound mole or the esteramide derived by reactionbetwoencquimolar portions or bis(hydromthyllacetamide and ricinoleicacid, is heated with one pound .mole of phthalic anhydride atapproximately 145-165"-C., until esteriflc aflon is complete, asindicated by the substantial elimination ofone alcoholichydroxylradical. Theprodnot so obtained has one free hydroxyl radical andonefreecarboxvl radical.

The following reaction will, serve to exemplify the formation of theforegoing compound: OHRCOOH indicatesricinoleic acid. 1

concoct on v Example 2 The product is prepared in the same manner asdescribed in the previous example, except that the substituted acetamideis derived from oleic acid instead of rieinoleic acid.

The following reaction will serve to exemplify the formation of theforegoing compound:

'RiCOOI-I indicates oleic acid.

canola noloc onto 3 cinioocai Example 3 The same procedure is followedas in Example 1, except that two moles of phthalic anhydride areemployed instead ofon'e mole, and'the final esterification product ischaracterized-by the sub-, stantial absence of any free hydroxyl radicaland by the presence of two free carboxyl radicals.

The following reaction will serve .to exemplify the formation of theforegoing compound:

' CHIOIH noloo cmca g cinioooao n B01000 I nooc Example ITrismydroxyinethyl) aminomethane is reacted with acetic acid to give acomparable substituted acetamide. Such acetamide is reacted with mm:

ole'ic acid to give an esteramide. Such esteramide is substituted inExamples 1 and 3, preceding.

The following reactions will serve to exemplify the formation of theforegoing compound:

The substituted acetamide derived from'bis- (hydroxymetyl) aminomethanein the manner de- 1 scribed in Examples, preceding, is reacted witholeic acid to give 'the corresponding esteramide.

Suchesteramideisconvortodintoanestermedf 4- 9,878,229 product in themanner described in Example 2, Example 8 preceding. In

- the preceding examples, where amylamine The following reactions willserve to exemplify is used as a reactant, cyclohexylamine or bowltheformation of the foregoing compound. 5 mine is substituted.

H The products obtained may be indicated in the 011.00011 HN%\ followingmanner:

cmon H000 onion g 7 N/OIHGOCQHiOOC-ROOC Ii omon noiocml Y iii I 3 n 0 nno 0 n I oimooimooanooc omens-c II H\ onto. OHaOOCJh a O Example 6Acetic acid is reacted with monoethanolamine Example' to give thecorresponding hydroxylated amide.

Such amide is then esterifled with ricinoleic acid In the precedingexamples, where oleic acid is to give the esteramide. Such esteramide isreemployed to introduce an acyloxy radical, naphacted with phthalicanhydride in equimolar prothenic acids, resin acids, or oxidized acidsare portions by an esteriflcation reaction to give the substituted.

esterifled final product having one free carboxyl In previous formulasfollowing under the headradical. ingof Example 2 and Example 5, if R1 isreplaced The following reactions will serve to exemplify so by R: withthe understanding that RzCOOH rept e formation f he r ng mp resents anaphthenie acid or a resin acid, then I n such formulas involving theuse of such radical cmcoon l R2, properly depict the composition.

' Example 10 In the preceding examples, where phthalic anhydride isused, maleic anhydride or oxalic acid is employed. In such instanceswhere oxalic acid is employed, it is desirable to use a lowertemperature, in view of the fact that oxalic acid, or

H cns mcimoln nolocaon HOOC , a temperature as high as 145 to 165 C., or

. Example 7 thereabouts, and instead a temperature of Acetic acid isconverted into the substituted 105-112 C. should be emplqy h lower amideby reaction with amylamine and then temperature requires longer t me foresteriflcatreated with two moles of ethylene oxide to give tion to takeplace:

the hydroxylolted amide. Such amide isthen re- As an illustration ofsome of the previous acted with ricinoleic acid to give the esteramide.formulas, the divalent radical I Such esteramide is then reacted withphthalic o H H anhydride in equimolar proportions tov give the -o=cfinal product having a free carboxyl radical.

The following reactions will serve to exemplify derived from maleicanhydride, replaces the dithe formation of the foregoing compound:valent aromatic radical :CcH4 derived from phthalic anhydride. cmcoonnlgclnll v 3000.03 0.11.03 noloo. a cmo.n +acimo cine. I 'f 3 CaH4OOOROHI n cimocimon nooocn i I 1 cimo n noloollnf cmoN cimo 0.1140 n noocaon gclmooonr 8000.011 cine.

I p cimo 1 5+ noloc. n

no '00 7o 7 CIHlQCR-Olfi nooocn clmoolmoooaon no oc r I omen v 11000. n

li c.n,, 7c Esteriflcationeanbeconductedintheumul most of its functionalequivalents, decompose at manner, simply employing heat to drive 01! thewater formed. In some instances, where manhydride is employed, water maynot be formed.

If desired, one may pass a dried, inert gas, such chamber through atrap. The xylene vapors carry oil the water, which is removed afterbeing condensedvby the trap. This is a conventional procedure, commonlyemployed in this type or similar types of reaction.

Although we preferto use phthalic anhydride as the most desirable sourceof the polybasic carboxy acid, one may use other polybasic carboxy acidsor their anhydrides, such as succinic, malic, fumaric, citric, maleic,adipic, tartaric, glutaric,

diphenic, naphthalic, oxalic, pimelic, suberic,

azelalc,'sebacic, etc. Naturally, a simple derivative of a polybasicacid, such as chlorophthalic acid, can be used as advantageouslyasphthalic acid itself, although there .is no added advantage in the useof the more costly chemical compounds. In view of the large number ofreactants and types of materials described, it may be well to note thosewhich we particularly prefer. It has been pointed out that we preferto'use unsaturated fatty acids as the source of the high molal acyloxyradical, and particularly the hyd oxylated fatty acids commonlyavailable, to wit, ricinoleicacid. We prefer to use phthalic. acid,maleic acid, or

their 'anhydrides, or oxalic acid as the source. of the polybasiccarboxy acid. We prefer to use acetic acid or its equivalent as thesource of the low molar acyl radical. We prefer to use monoethanolamineor diethanolamine' as the reactant for formation of the ubstituted amideemployed for subsequent reaction'to produce the esteramide.

In view of what has been said, it is apparent that the hydroxylatedesteramides of the kind described previously may be considered, forthe Isake of simplicity, as being inrthe class of an alcohol, i. e., amonohydric or polyhydrlc alcohol. If

an alcohol is indicated by the formula Y'fOH) 1|,

where 11 indicates the number one or more, and if a polybasic acid bodybe indicated by the formula X'KCOOH) I, where n indicates the number '2or more, then the reaction between a monohydric alcohol and a polybasicacid will result in a compound which may be indicated by the followinformula; .Yxwoon v, where 1: indicates the number one or more, and whichis in reality a 1 contraction of a more-elaborate structural formula, inwhich x' andY' are joined by a carboxylradical or residue.nssumingrhowever, as

would be true in the majority of cases, that the alcohol actually wouldbe a polyhydric alcohol, and that the acid body would be a polybasic ina nature, for instance, if one employed a diphthaiate" of a plyhydroxylated esteramide of the kindpreviously described, thenexamination reveals that formula mightresult in a combination. inwhichthere were neither residual carboxyl radiicals, nor residual hydroxylradicals, or might resuit-in compounds in which there were residualhydroxyl radicals, and no residual carboxyl radi-f cals, or oo'mpoimdswhere there misht be I V carboxyl-radicals and noresidualhydrcsyl-ra'di- 75 there is present either an unelteriiiedhydroxyl bythc following formula:

818} or there might be both. This is, indicated by the following: a

' s(OH)1u (YX) @(COOH) m' (on) warm @(00011) 1..

in which a indicates a small whole number (one in the case of a monomer,and probably not over 20 and usually less than and m and n indi- 10cate'the number 1 or more, and m" and n" indicate zero or a small ormoderately sized whole number, such as zero, one or more, but in anyevent, probably anumber not in excess of 10-15. Naturally, each residualhydroxyl could combine with a phthalic acid body or its equivalent, orwith a similar compound derived from a tribasic acid, such ascitricacid; and in such event, there would 1 be a large number of free oruncombined c'arbo'xyl radicals present, possibly or more. Actually, I

the preferable type of reagent would be more apt to include less than20, and in fact, less than 10 free hydroxyl radicals. It is notnecessaryto r-' mark that the residual carboxyl radicals can bepermitted to remain as such, or can be neutralized in any suitablemanner, such as conversion into salts, esters,'amides, amino esters, orany'other suitable form. Usually; such conversion into salt form wouldbe by mean of sodium hydroxide, potassium hydroxide, calcium hydroxide,magnesium hydroxide, ammonium hydroxide, amylamine, butanoiamine,ethanolamine, dlethanolamine, triethanolamine, cyclohexanolamine,benzylamine, aniline, toluidine, etc. Conversion into the ester would beby means ofa monohydricalcohol, suchas methylalcohol, ethylalcohol,propyl alcohol, butyl' alcohol, hexyl alcohol, octyl alcohol, decylalcohol, ethylene. glycol, diethylene glycol, glycerol, diglycerol,triethylene glycol,- or

the, like. One could employ an amino alcohol so new produc'e an ester.-

definite extent; for instance, at least 5% in some solvent such aswater, alcohol, benzene, dichlorethyl ether, acetone, cresylic acid, orthe like.

This is simply another way of stating that it is preferable, if theproduct be one of the sub-resins, which are commonly referred to as an Aresin, or

Breain, as distinguished from'a C resin, which is a highly infusible,insoluble resin (see- Ellis,

Chemistry of Synthetic Resins," 1935, p ge 862, et seq.)..- Inrecapitulating what has been said previously. a the sub-resinous,semi-resinous, or balsam-like product herein "contemplated may minim-area decorat not greater than 5,'and 2' represents a small whole number notgreater than .5; Z represents a hydrogen equivalent, such as a metallicatom,

It-wlll be noted that compounds of the type ius't describedhavingjat'leaet'one hydrophobe nucleus are designated as "polar when We havefound, however, as suggested, that the.-

be indicated greater eiiectiveness as a demulsifler.

radical, or an unesterifled carboxyl radical, or both. We have foundthat the polar type of material is by far the most effective fordemulsiflcation, and it is our preference to use such type. Indeed, thisparticulartype is so much more effective for demulsiflcation than thenon-polar type, that it may be considered in essence an ln-' ventionwithin an invention.

The presence of a low molal acyl group, par-' ticularly when derivedfrom a. non-hydroxyacid,

such as acetic acid, butyric acid, and the like, has a definitefunctional effect that is difllcult to explain. In numerous instancesthe presence of such radical in the selected compound, instead of anamino hydrogen atom, results in markedly One possible explanation mayreside in the fact that the presence of an amino hydrogen atom or thepresence of two amino hydrogen atoms, ordinai ily may contribute toassociation in the presenceof hydroxylated compounds; to a greaterextent than when an acyl radical of the kind described is present as asubstituent for an amino hydrogen atom. Regardless of whatever thecorrect explanation may be, the effectiveness ofthe new compounds asdemulsiflers in co'mparisonwith kindred compounds, is readilydemonstrable.

acre-ma Compounds of the kind herein contemplated may be used asplasticizers or softening agents in the manufacture of resin-likematerials. They are also of distinct value as a break inducer in. thedoctor treatment of gasoline or the like, as described in U. S. PatentNo. 2,137,223, to Sutton, dated May 9, 1939.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A sub-resinous ester of the following formula:

coon).

(OH)-(Y,'X.') 0001 in which :0 and y are small whole numbers not greaterthan 10 and m, n, and m are small whole numbers not over 10, andincluding zero; Z is acation; X is the polycarboxy acid radical of apolycarboxy acid having less than 4 carboxyl radicals and less than 15carbon atoms, and Y is a hydroxylated esteramide radical containing inturn: (a) an 'amido-linked saturated low molal monocarboxy acid acylradical having not over 5 4. The ester described in claim 1,

viso that X be joined to Y by an ester linkage only. i

2. The ester described in claim 1, wherein the low molal monocarboxyacid acyl radical contains oxygen atoms united to the carbonyl carbonatom only.

3. The ester described in claim 1, wherein the low molal monocarboxyacid acyl radical contains oxygen atoms united to the carbonyl atom onlyand that the polycarboxy acid be a dicarboxy acid.

wherein the low molal monocanboxy acid acyl radical contains oxygenunited to the carbonyl atom only and that the polycarboxy acid be adicarboxy acid, and that RCO be that of a higherfatty acid radical.

5. The ester described in claim 1, wherein the low molal monocar-boxyacid acyl radical contains oxygen atoms united to the carbonyl atom onlyand that the polycarboxy acid be a dimboxy acid, and that RCO be that ofa higher unsaturated fatty acid.

6. The ester described in claim 1, wherein the low molal monocarboxyacid acyl radical con-- tains oxygen atoms united to the carbonyl atomonly and that the polycarboxy acid be a dicarboxy acid, and that RCO bethat of ricinoleic acid.

t '7. The ester described in claim 1, wherein the low molal monocarboxyacid acyi radical contains oxygen atoms united to the carbonyl atom onlyand that the polycarboxyacid be phthalic acid, and that RCO be that ofricinoleic acid.

8. The ester described in claim 1, wherein the low molal monocarboxyacid acyl radical contains oxygen atoms united to the carbonyl atom onlyand that'the polycarboxy acid be maleic acid,

and that RCO be that of ricinoleic acid.

9.- The ester described in claim 1, wherein the low molal monocarboxyacid acyl radical contains oxygen atoms united to the carbonyl atom onlyand that polycarboxy acid be oxalic acid, and that RCO be that ofricinoleic acid.

10. In a. method for the manufacture of esters described in claim 1, thestep of esterifymil (A) a hydroxyiated esteramide I containing (a) anamideo-linked saturated low molal monocarboxy acid acyl radical havingnot over 5 carbon atoms:

carbon atoms; and (b) at least one monocarboxy detergent-forming acidacyloxy radical RCO having at least 8 and not more than 32 carbon atoms,

' and linked by a, divalent aliphatic radical-to the amido nitrogenatom; and with the added proand (b) at least one monocarboxydetergentforming acid acyloxy radical having at" least 8 and not morethan 32 carbon atoms and linked by a divalent aliphatic radical to theamido nitrogen atom, with (B) a polybasic carbon acid.

MELVIN DE GROOTE. BERNHARD KEISER.

